CN114559725A

CN114559725A - High-formability gold-plastic composite film, laminated body and battery

Info

Publication number: CN114559725A
Application number: CN202210172189.7A
Authority: CN
Inventors: 庄志; 黎秋生; 王小明; 虞少波; 张茜; 程跃
Original assignee: Jiangsu Ruijie New Material Technology Co ltd
Current assignee: Jiangsu Ruijie New Material Technology Co ltd
Priority date: 2022-02-24
Filing date: 2022-02-24
Publication date: 2022-05-31
Anticipated expiration: 2042-02-24
Also published as: CN114559725B

Abstract

The invention relates to the field of battery external packaging, and particularly discloses a high-formability gold-plastic composite film which comprises an external base material resin layer, an intermediate metal layer and an internal heat-sealing resin layer; the outer base material resin layer at least has a multi-layer co-extrusion structure of a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer), wherein the layer a contains crystalline polyester, the layer b contains at least two of acid modified polyolefin, sulfogroup-containing polyester and modified polyester elastomer, and the layer c contains at least one of aliphatic polyamide and aromatic polyamide. The battery using the flexible package aluminum plastic film with the structure not only realizes the thinning and lightening of the outer packaging material for the battery, but also has excellent performances such as formability, insulativity, dimensional stability and the like.

Description

High-formability gold-plastic composite film, laminated body and battery

Technical Field

The invention relates to the technical field of production of external packages of soft package batteries, in particular to a high-formability gold-plastic composite film, a laminated body and a battery.

Background

In the prior art, various types of batteries have been developed, and in these batteries, battery elements such as electrodes and electrolytes are required to be packaged with a packaging material. In recent years, with the increase in performance of cameras, electric vehicles, hybrid electric vehicles, and the like, batteries are required to have high performance, as well as to be thin and lightweight. Therefore, the lithium ion battery with flexible package aluminum plastic film is more and more paid attention and applied.

The flexible packaging aluminum plastic film is generally formed by compounding three films with different functions, wherein the outer layer is an outer base resin layer formed by polyamide (hereinafter referred to as PA) or polyethylene terephthalate (hereinafter referred to as PET) and the like and is used as a protective layer, the middle layer is a metal layer and is used as a barrier layer, and the inner layer is an inner heat welding resin layer. At present, a flexible packaging aluminum plastic film is provided, wherein a base material resin layer of the flexible packaging aluminum plastic film is a two-layer composite structure formed by bonding PA and PET through an adhesive, and the battery using the flexible packaging aluminum plastic film with the structure realizes the light weight of the battery and simultaneously optimizes the service performance of the battery. However, since the base resin layer is a two-layer composite structure formed by bonding PA and PET with an adhesive, the thickness of the aluminum-plastic film is increased, the production process is complicated, and the increase of the process inevitably leads to the increase of the cost. In addition, as another method, a co-extrusion method may be used in which PA and PET are co-extruded to form a film as an outer base resin layer. However, the peel strength of PA and PET films produced by conventional coextrusion methods is not sufficient, and delamination between PA and PET may occur during long-term storage, particularly when stored under high humidity conditions. When the protective layer is used as a protective layer, the external insulation of the battery is deteriorated and the life of the battery is shortened when the insulation is low. Further, the film may have pinholes due to strong impact from the outside. Therefore, its function as a protective layer is insufficient, which is problematic.

Disclosure of Invention

The present invention has an object to overcome the disadvantages of the prior art and to provide a laminate for a battery outer packaging material, which is thin and lightweight, low in cost, high in strength, high in weather resistance, high in insulation properties, and high in moldability.

The purpose of the invention is realized by the following technical scheme:

the invention aims to provide a high-formability gold-plastic composite film, which comprises an outer base resin layer, an intermediate metal layer and an internal heat welding resin layer; the outer base resin layer has at least a multi-layer co-extrusion structure of a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer), wherein,

the layer a contains a crystalline polyester and the layer b contains a crystalline polyester,

the layer b comprises at least two of acid modified polyolefin, sulfo-containing polyester and modified polyester elastomer,

the layer c contains at least one of aliphatic polyamide and aromatic polyamide.

Further, the anti-corrosion coating also comprises a first anti-corrosion layer formed on the side, in contact with the internal heat welding resin layer, of the intermediate metal layer.

Still further, a first adhesive layer is arranged between the first anti-corrosion layer and the inner heat welding resin layer; and a second adhesive layer is arranged between the outer substrate resin layer and the middle metal layer.

Further, a second anti-corrosion layer is arranged on one side, in contact with the second adhesive layer or the outer base material resin layer, of the middle metal layer.

Further, the total thickness of the a layer/b layer/c layer co-extrusion structure is less than 50 μm.

Further, in the multi-layer co-extrusion structure consisting of the a layer/b layer/c layer, the b layer is formed by a single layer or multiple layers.

Further, when the layer b contains an acid-modified polyolefin and at least one of a modified polyester elastomer and a sulfo-containing polyester, the layer b is composed of a plurality of layers, and the acid-modified polyolefin is on the side in contact with the layer c.

Specifically, when the layer b contains acid-modified polyolefin, modified polyester elastomer and sulfogroup-containing polyester, the layer b has a multilayer structure of acid-modified polyolefin/modified polyester elastomer/sulfogroup-containing polyester or a multilayer structure of acid-modified polyolefin/(blend layer of modified polyester elastomer and sulfogroup-containing polyester), and the acid-modified polyolefin is in contact with the layer c.

More specifically, the layer b contains acid modified polyolefin, modified polyester elastomer and sulfogroup-containing polyester, the layer b is a multilayer structure of acid modified polyolefin/(modified polyester elastomer and sulfogroup-containing polyester blended layer), and the thickness of the layer b is 1-

3μm。

Further, when the layer b contains the modified polyester elastomer and the sulfo-containing polyester and does not contain the acid-modified polyolefin, the layer b is composed of a single layer or a plurality of layers.

Specifically, when the layer b is composed of a single layer, the single layer is a blend layer of a modified polyester elastomer and a sulfopolyester.

Specifically, when the b layer is composed of a plurality of layers, each of the plurality of layers is a blend layer of a modified polyester elastomer and a sulfo-containing polyester.

The peel strength between the layer a and the layer c of the high-formability gold-plastic composite film is more than 2.6N/15mm, preferably more than 3.2N/15mm in terms of the peel speed of 50mm/min under the environment that the temperature is 23 ℃ and the relative humidity is 50% +/-5%.

The peel strength between the layer a and the layer c of the high-formability gold-plastic composite film is more than 1.0N/15mm, preferably more than 1.9N/15mm, in terms of the peel speed of 50mm/min under the environment that the temperature is 40 ℃ and the relative humidity is 90% +/-2%.

Placing any one of the high-formability gold-plastic composite films for 24 hours in an environment with the temperature of 23 ℃ and the relative humidity of 50% +/-5%, and then placing

Electrode cylinder and

the dielectric breakdown voltage of the highly moldable composite gold-plastic film is 0.1kV/μm or more, preferably 0.12kV/μm or more, with respect to the total thickness of the highly moldable composite gold-plastic film, by performing breakdown at a voltage-increasing rate of 0.3 kV/sec.

Any one of the highly moldable composite gold-plastic films described above is allowed to stand at a temperature of 23 ℃ and a relative humidity of 50% +/-5% for 24 hours, and then subjected to a puncture strength test at a test speed of 50mm/min using a test needle having a tip R0.5mm, and the puncture strength with respect to the total thickness of the highly moldable composite gold-plastic film is 0.15N/μm or more, preferably 0.2N/μm or more.

The depth of penetration of any one of the above-mentioned high-formability gold-plastic composite films is 4.5-10.0mm, preferably 6.0-10.0 mm.

It is a second object of the present invention to provide a laminate applied as an outer base resin layer to a gold-plastic composite film; the laminate has a multilayer co-extrusion structure of at least a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer), wherein,

Here, the laminate is an outer base resin layer in one of the objects of the present invention.

Further, the laminate is allowed to stand at 23 ℃ and a relative humidity of 50% +/-5% for 24 hours, and then subjected to a heat treatment

Electrode cylinder and

the breakdown voltage with respect to the thickness of the laminate is 0.23kV/μm or more, preferably 0.25kV/μm or more.

Further, the laminated body is placed for 24 hours in an environment with the temperature of 40 ℃ and the relative humidity of 90% +/-2%, so as to

Electrode cylinder and

the breakdown is performed at a voltage increase rate of 0.3kV/sec, and the dielectric breakdown voltage with respect to the thickness is 0.15kV/μm or more, preferably 0.17kV/μm or more.

Further, the laminate is left to stand at a temperature of 23 ℃ and a relative humidity of 50% ± 5 for 24 hours, and then subjected to a puncture strength test at a test speed of 50mm/min using a test needle having a tip r0.5mm, and the puncture strength with respect to the thickness is 0.65N/μm or more, preferably 0.67N/μm or more.

It is another object of the present invention to provide a battery comprising the highly moldable gold-plastic composite film as an outer packaging material for a battery.

Compared with the prior art, the invention has the following positive effects:

the outer base resin layer of the high-formability laminated body for the gold-plastic composite film is formed by a multi-layer co-extrusion structure at least comprising 3 layers of a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer), and the total thickness of the outer base resin layer is not more than 50 mu m. The battery using the flexible package aluminum plastic film with the structure not only realizes the thinning and lightening of the outer packaging material for the battery, but also has excellent performances such as formability, insulativity, dimensional stability and the like.

Compared with other materials, the outer base material resin layer adopts a multi-layer co-extrusion film forming method, and compared with a dry compounding method, the method has the advantages of engineering simplification and ensures the stability and the service performance of the material more excellently. Meanwhile, as a packaging material for batteries, the characteristics of thickness and lightness and thinness of the packaging material also meet the requirements and development trends of the materials at present. In addition, the laminate for a battery outer packaging material provided by the present invention has a positive effect on cost reduction while reducing the total thickness of the battery outer packaging material and simplifying the production process thereof.

Drawings

FIG. 1 is a schematic structural diagram of a high moldability gold-plastic composite film according to an embodiment of the present invention;

FIG. 2 is a schematic structural diagram of another high moldability gold-plastic composite film according to an embodiment of the present invention;

FIG. 3 is a schematic structural diagram of another high moldability gold-plastic composite film according to an embodiment of the present invention;

FIG. 4 is a schematic structural view of the gold-plastic composite films according to examples 1 to 8 and comparative examples 1 to 9 of the present invention;

FIG. 5 is a schematic structural view of an outer substrate resin layer according to an embodiment of the present invention;

FIG. 6 is a graph of test data of the structures and evaluation items of examples 1 to 11 of the present invention and comparative examples 1 to 9;

reference numerals:

1-an outer substrate resin layer; 2-a second adhesive layer; 3-intermediate metal layer; 4-a first adhesive layer; 5-inner heat welding resin layer; 6-a first corrosion resistant layer; 7-a second corrosion resistant layer; 8-a coloring layer; a-a polyester layer; b-an adhesive layer; c-a polyamide layer; -nylon 6; MXD 6; a-an acid-modified polyolefin; b-a sulfo-containing polyester; a C-modified polyester elastomer.

Detailed Description

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to examples. Before the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is intended as a preferred example for purposes of illustration only and is not intended to limit the scope of the present disclosure, so it is to be understood that other equivalents and modifications may be made without departing from the spirit and scope of the present disclosure.

[ highly-molded packaging Material for Metal-Plastic composite film for Battery elements ]

1. Laminated structure of high-forming gold-plastic composite film

As shown in figure 1, the high-molding gold-plastic composite film is formed by sequentially laminating at least an outer base resin layer 1, an intermediate metal layer 3 and an inner heat-sealing resin layer 5, wherein the battery element is enclosed in a closed space by the gold-plastic composite film, the outer base resin layer 1 is the outermost side, and the inner heat-sealing resin layer 5 is the inner side which is in contact with the battery element.

As shown in fig. 2, in order to improve the bonding force between the laminated structures of the gold-plastic composite film, the gold-plastic composite film of the present invention may further include a second adhesive layer 2 between the outer base resin layer 1 and the intermediate metal layer 3, and/or a first adhesive layer 4 between the intermediate metal layer 3 and the inner heat-fusible resin layer 5.

As shown in fig. 3, in order to change the appearance color of the packaging material for lithium ion battery elements, a colored layer 8 may be provided between the outer base resin layer 1 and the intermediate metal layer 3, in the first adhesive layer 4, or outside the outer base resin layer 1, and a colored layer 8 may be provided.

As shown in fig. 3 or 4, in order to improve the corrosion resistance of the gold-plastic composite film, the gold-plastic composite film of the present invention has a first corrosion-resistant layer 6 formed at least on the metal surface side of the intermediate metal layer 3 adjacent to the internal heat-sealing resin layer 5, i.e., the gold-plastic composite film of the present invention may be formed by sequentially laminating at least an outer substrate resin layer 1, the intermediate metal layer 3, the first corrosion-resistant layer 6, and the internal heat-sealing resin layer 5. Further, the second corrosion-resistant layer 7 may be formed on the metal surface side of the intermediate metal layer 3 close to the outer base resin layer 1.

The possible individual layer structures will be explained below.

1.1 outer base resin layer (i.e. laminate in the independent claim of the invention) 1

The outer base material resin layer 1 of the present invention has a multi-layer co-extrusion structure having insulation properties in conformity with the function of the outer base material and having at least a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer).

The outer substrate resin layer 1 can be adhered to the intermediate metal layer 3 by one or a combination of extrusion, coating, compounding and heat pasting, and the total thickness of the outer substrate resin layer 1 is less than 50 μm. If it exceeds 50 μm, the total thickness of the gold-plastic composite film becomes too large and the flexibility becomes poor.

1.1.1 preparation of outer substrate resin layer 1

In the multi-layer co-extrusion structure of the polyester layer (a layer)/the adhesive layer (b layer)/the polyamide layer (c layer) of the outer base resin layer 1 of the present invention,

Here, the crystalline polyester in the a layer is preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or a combination of both. The thickness of the a layer is preferably 2 to 15 μm, and when the thickness of the a layer is less than 2 μm, the insulation property and weather resistance are poor, and when it exceeds 15 μm, the elongation of the outer base resin layer is deteriorated, and the moldability of the gold-plastic composite film is lowered.

Here, the layer b is composed of a single layer or a plurality of layers, and contains at least two of an acid-modified polyolefin, a sulfo-containing polyester, and a modified polyester elastomer. Among them, the acid-modified polyolefin is preferably 15% by weight or more.

The acid-modified polyolefin in the layer b is a polymer modified by block polymerization or graft polymerization with a polyolefin using an acid component. As the acid-modified polyolefin, a copolymer obtained by copolymerizing the above polyolefin with a polar molecule such as polyacrylic acid or methacrylic acid, or the like, may be used. As the acid component used for acid modification, carboxylic acids or sulfonic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, and anhydrides thereof can be used, and acrylic acid or maleic acid and anhydrides thereof are preferred.

The modified polyester elastomer in the layer b is obtained by introducing a polar functional group having a high affinity with the polyester resin into the polyester elastomer, and the polar group used for modifying the polyester may be an amino group, a hydroxyl group, a carboxyl group, an epoxy group, an amide group, or the like, preferably an epoxy group or an amide group.

The layer b contains at least two of acid modified polyolefin, sulfo-containing polyester and modified polyester elastomer. The acid-modified polyolefin may be combined with the sulfo-containing polyester and/or the modified polyester elastomer, or may be combined with the sulfo-containing polyester and the modified polyester elastomer.

The combination of the layer b of acid-modified polyolefin and the sulfo-containing polyester and/or the modified polyester elastomer is a multilayer structure, and the acid-modified polyolefin is on the contact side of the layer c. The acid modified polyolefin reacts with the layer c and is then compatible with the layer a, so that the problem that the acid modified polyolefin has good adhesion with the layer c only and the sulfo polyester and/or modified polyester elastomer has good adhesion with the layer a only is solved, and the performances such as peel strength, weather resistance, forming limit and the like are improved.

The combination of the sulfopolyester and the modified polyester elastomer in the layer b can be a multilayer structure or a single-layer structure, and the sulfopolyester and the modified polyester elastomer can be separately mixed for use in a layered manner or can be used in a blended manner. The polyester main chain can be compatible with the layer a for adhesion, the modified polar group can well react with the layer c for adhesion, the peel strength is improved, and the contained sulfo group captures and absorbs a small amount of water permeating from the layer b of the cross section in a high-humidity or high-temperature wet environment, so that the direct corrosion of the modified polar group by the water and the reaction adhesion of the layer c are avoided. The performances such as peeling strength, weather resistance, forming limit and the like are improved.

The thickness of the layer b is 1 to 3 μm, preferably 1 to 2 μm or 2 to 3 μm, and is exemplified by 1 μm, 1.5 μm, 2 μm, 2.5 μm, and 3 μm. When the thickness is less than 1 μm, the b layer does not have sufficient cohesive strength, and when the thickness exceeds 3 μm, the cross-sectional area permeates water to increase and the weather resistance is lowered when it is left in the environment.

Here, the aliphatic polyamide in the layer c is preferably nylon 6, the aromatic polyamide is preferably polyamide MXD6, or a combination of both. The thickness of the c layer is preferably 5 to 50 μm, and when the thickness of the c layer is less than 5 μm, moldability and insulation are not good, and when the thickness exceeds 50 μm, the thickness is too thick, which results in poor flexibility of the outer base resin layer and a reduction in lightweight and thin values.

1.1.2 external base resin layer 1 surface or/and internal additives

One or more additives such as a lubricant, a flame retardant, an anti-blocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent may be added to the surface or/and the interior of the outer base resin layer 1.

Among them, from the viewpoint of improving the moldability of the packaging material for lithium ion battery elements, it is preferable to form a layer made of a lubricant on the surface layer of the outer base resin layer 1. The lubricant is not particularly limited, and may be used singly or in combination of two or more kinds, and the lubricant is preferably an amide-based lubricant.

Wherein the amide lubricant comprises saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylol amide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, fatty acid amide, aromatic bisamide and the like; among them, as examples of the saturated fatty acid amide, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, and the like; examples of the unsaturated fatty acid amide include oleamide, erucamide and the like; substituted amides include N-oil palmitamide, N-stearamide, N-oil stearamide, and N-stearamide; methylol amides including methylol stearic acid amide and the like; saturated fatty acid bisamides include methylene bisstearamide, ethylene bisoctanoamide, ethylene bislauric amide, ethylene bisstearamide, ethylene bishydroxystearamide, ethylene bisbehenamide and hexamethylene bisstearamide, hexamethylene hydroxystearamide, n '-distearyladipamide, n' -distearylsebacic amide, and the like; unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucamide, hexamethylene bisoleic acid amide, n '-dioleyl adipic acid amide, and n, n' -dioleyl sebacic acid amide. Fatty acid ester amides including stearamide ethyl stearate and the like; the aromatic bisamide includes m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, n' -distearyl isophthalic acid amide and the like.

The lubricant present on the surface of the outer base resin layer 1 may be a lubricant exuded from the outer base resin layer 1 containing a lubricant as a constituent material, or a lubricant may be applied to the surface of the outer base resin layer. Specifically, when a lubricant is present on the surface of the outer base resin layer 1, the amount of the lubricant to be applied is not particularly limited, but is preferably applied at about 3mg/m²Above, more preferably 4 to 30mg/m²Left and right.

1.2 second adhesive layer 2

In the packaging material for a lithium ion battery element of the present invention, in the case where the outer base resin layer 1 and the intermediate metal layer 3 are laminated, a second adhesive layer 2 may be optionally provided, and the second adhesive layer 2 may be a single layer or a multilayer laminate of adhesive layers.

The thickness of the second adhesive layer 2 is not particularly limited as long as the outer base resin layer 1 and the intermediate metal layer 3 can be bonded to each other, and a preferable range is about 1 to 10 μm, and more preferably about 2 to 5 μm.

1.2.1 Components of the second adhesive layer 2

The second adhesive layer 2 is not particularly limited, and the second adhesive layer 2 is a layer formed for the purpose of improving the adhesion between the outer base resin layer 1 and the intermediate metal layer 3, and mainly contains a binder, and may be a two-component curing type binder or a one-component curing type binder; on the other hand, the adhesive may be any of a chemical reaction type, a solvent volatilization type, a hot melt type, a hot press type, and the like.

Wherein, when the adhesive is a bi-component curing adhesive, the adhesive comprises a main agent and a curing agent; the base compound may be any one or a combination of plural kinds of polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene isophthalate and copolyester, polyamide resins such as polyether resins, polyurethane resins, epoxy resins, phenol resins, nylon 6, nylon 66, nylon 12 and copolyamides, polyolefin resins such as polyolefin, cyclic polyolefin, acid-modified polyolefin and acid-modified cyclic polyolefin, amino resins such as polyvinyl acetate, cellulose, (meth) acrylic resins, polyimide resins, polycarbonate, urea resins and melamine resins, rubbers such as chloroprene rubber, nitrile rubber and styrene-butadiene rubber, and silicone resins; the curing agent is selected according to the functional group of the adhesive component, and is appropriately selected from a polyfunctional epoxy resin, a methanesulfonic acid-containing polymer, a porlyamine resin, an inorganic acid, and the like.

Preferably, the binder used in the second adhesive layer 2 of the present invention is: the two-component polyurethane adhesive is formed by using polyester polyol, polyurethane modified polyol and the like as main diol agents and aromatic or aliphatic isocyanate as a curing agent.

Alternatively, the binder used in the second adhesive layer 2 of the present invention is preferably: one or two of binary or multi-component polyester and polyurethane modified polyester, and isocyanate. Among these, isocyanates are not particularly limited to compounds having two or more isocyanate groups in the molecule, and examples thereof include one or a mixture of two or more of polymers such as isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI), and 1, 6-Hexamethylene Diisocyanate (HDI).

1.2.2 production of the second adhesive layer 2

Coating the slurry containing the binder between the intermediate metal layer 3 and the outer base resin layer 1, heating for a certain time at a certain temperature to volatilize the organic solvent in the slurry to form a second adhesive layer 2, further compounding the outer base resin layer 1, the second adhesive layer 2 and the intermediate metal layer 3 at a certain temperature and pressure, storing for a certain time at a certain temperature, and then curing the second adhesive layer 2 to obtain the outer base resin, wherein the composite resin layer is composed of the outer base resin 1, the second adhesive layer 2 and the intermediate metal layer 3.

1.2.3 additives on the surface or/and inside the second adhesive layer 2

The second adhesive layer 2 may contain a colorant, a thermoplastic elastomer, a tackifier, a filler, and the like, as long as it does not inhibit adhesiveness and allows addition of other components.

The second adhesive layer 2 contains one or more colorants, whereby the packaging material for lithium ion batteries can be colored, and colorants such as pigments and dyes can be used; the type of the pigment is not particularly limited as long as the adhesiveness of the outer layer adhesive layer is not impaired; the average particle diameter of the pigment is not particularly limited, and may be selected from about 0.05 to 5 μm, preferably about 0.08 to 2 μm (the average particle diameter of the pigment is the median diameter measured by a laser diffraction/scattering particle size distribution measuring device), and the content of the pigment is not particularly limited as long as the packaging material for lithium ion battery elements is colored, preferably about 5 to 60%, more preferably 10 to 40%. Specifically, as the organic pigment, for example, pigments of azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, thioindigo, perylene, isoindoline and the like; as the inorganic pigment, carbon black-based, titanium oxide-based, cadmium-based, lead-based, isoindoline-based pigments and the like; among these, carbon black is preferable in order to make the appearance of the packaging material for lithium ion battery elements black.

1.3 "" colored layer 8 "

In addition to the addition of the colorant to the second adhesive layer 2, the packaging material for lithium ion battery elements of the present invention may be provided with a colored layer 8 between the outer base resin layer 1 and the intermediate metal layer 3, or outside the outer base resin layer 1.

1.3.1 composition of the coloured layer 8

The coloring layer 8 mainly contains a coloring agent, which may be a pigment or a dye, and may be used alone or in combination of two or more; as a specific example of the coloring agent contained in the colored layer, reference may be made to the above-mentioned example of the coloring agent in the second adhesive layer 2.

1.3.2 preparation of the coloured layer 8

The colored layer 8 is not particularly limited, and may be formed by applying ink containing a colorant to the surface of the outer base resin layer 1, the surface of the second adhesive layer 2, or the surface of the intermediate metal layer 3.

1.4 "" intermediate metal layer 3 ""

The intermediate metal layer 3 referred to in the present invention is a barrier layer that can at least suppress the penetration of moisture into a highly moldable and highly durable exterior material for a battery element.

1.4.1 composition and content of intermediate Metal layer 3

The intermediate metal layer 3 is an aluminum alloy foil containing Fe, Si, Sb and Cu and annealed. The grain size and size deviation of the intermediate metal layer can be reduced by controlling the amounts of Sb and Si, and the strength and the elongation are improved; by controlling the amount of Cu, it is also effective to improve the strength of the aluminum alloy foil of the intermediate metal layer, and increasing the amount of Cu increases the strength, and plays a positive role in forming.

Improve the content of Cu and be good for the shaping, but increase the risk of corruption, can effectively prevent to take place the corruption through setting up inside and outside anti-corrosion coating, but in the past after adding the alloy composition, can lead to aluminium alloy foil surface to separate out the alloy, and then influence the volatilization of rolling oil, if aluminium alloy foil surface rolling oil does not volatilize totally, under the condition that aluminium alloy foil surface cleanliness factor is low, can influence follow-up inside and outside anti-corrosion coating's effect promptly, lead to the peel strength low, so need be in certain within range with alloy composition control, reach the mesh that both can improve aluminium alloy foil's formability, can not separate out alloy composition again and influence follow-up coating. Meanwhile, the cleanliness of the surface can be managed by a method using a wetting agent test wettability as an index or a method using a contact angle as an index. The index of wettability is D class or more, preferably B class. In addition, as an index of the contact angle, the contact angle is 25 or less, preferably 20 or less, more preferably 15 or less, and further 10 or less in the pure water test. When the wettability is lower than C or the contact angle exceeds 25, the reactivity with an anticorrosive layer described later or initial adhesion is deteriorated. If the reactivity deteriorates and the reaction of the second corrosion-resistant layer 7 or the first corrosion-resistant layer 6 with the intermediate metal layer 3 becomes insufficient, the resistance to permeation of the electrolytic solution as the battery content and the resistance to hydrogen fluoride generated in the reaction of the electrolyte with water decrease. As time passes, the adhesion of the second corrosion-resistant layer 7 or the first corrosion-resistant layer 6 to the intermediate metal layer 3 is reduced, the corrosion-resistant layer is dissolved, and the intermediate metal layer 3 and the second corrosion-resistant layer 7 or the first corrosion-resistant layer 6 may peel off, thereby shortening the life of the battery. The same applies to the case where the initial adhesion between the second corrosion-resistant layer 7 or the first corrosion-resistant layer 6 and the intermediate metal layer 3 is deteriorated. The present invention can suppress the precipitation of alloy from an aluminum alloy foil by adjusting the alloy composition and controlling the alloy ratio within a certain range. In addition, in the annealing step during rolling, the temperature and time conditions can be easily controlled. In summary, by limiting the content combinations of the four elements of Fe, Si, Sb, and Cu in the aluminum alloy foil, the management of the surface cleanliness is facilitated, the durability, i.e., the electrolyte resistance is stabilized, and the service life of the battery is prolonged. The surface wettability test of the aluminum alloy foil layer can adopt the national standard GB/T225638.5-2016 of the people's republic of China, the aluminum foil test method, and the 5 th part, the wettability test. In addition, the contact angle test of the aluminum alloy foil layer can adopt the national standard GB/T22638.9-2008 of the people's republic of China, part 9 of the aluminum foil test method, hydrophilicity measurement.

When the content of Si in the aluminum alloy foil exceeds 0.1%, the crystal grain size becomes large, the grain size deviation becomes large, the tensile strength is lowered, and the formability is deteriorated; when the content of Sb in the aluminum alloy foil exceeds 0.06%, the tensile strength and the tensile rate tend to be stable, no obvious positive effect on formability is generated, the toxicity of a finished product is increased, and the actual practicability is influenced; when the content of Fe in the aluminum alloy foil exceeds 1.7%, excessive Fe is precipitated because it cannot form a compound with Si or Al, so that the tensile strength of the aluminum alloy foil is reduced and formability is deteriorated; excessive Fe easily causes corrosion and discoloration, and influences the electrolyte resistance of the composite membrane; when the Cu content in the aluminum alloy foil exceeds 0.65% and the Cu content exceeds 0.5 when the Fe content is 1, the aluminum alloy foil is easily corroded, which affects the electrolyte resistance of the composite film.

Specifically, the content of Fe in the aluminum alloy foil is less than 1.7%; the Si content is 0.1% or less, preferably 0.05% or less; the Sb content is 0.06% or less, preferably 0.05% or less; the Cu content is more than 0.003 percent, the upper limit is 0.65 percent, and the Cu content is preferably more than 0.01 percent; more preferably, the content of Si is 0.09 or less, more preferably 0.07 or less, and the content of Cu is 0.5 or less, when the content of Fe is 1.

1.4.2 physical Properties of intermediate Metal layer 3

In the present invention, when rolling an aluminum alloy foil, the direction perpendicular to the axial direction of the rolling roller (the direction in which the aluminum alloy foil travels) is the MD direction; the direction parallel to the axial direction of the rolling roller (the direction orthogonal to the MD direction) is the TD direction; the 45 of TD indicates a direction at 45 ° to the TD direction.

The present invention emphasizes that when the TD 45 of the aluminum alloy foil has a tensile strength in the MD direction of 80MPa or more, an elongation at break of 10% or more, and a 0.2% proof stress of 35MPa or more, the difference between the tensile strength in the TD 45 of the aluminum alloy foil in the MD direction and the elongation at break is called anisotropy, and the smaller the anisotropy, the more advantageous the formability of the composite film is. And when the tensile strength of the aluminum alloy foil is too small, the composite film is easy to deform after being formed when being subjected to external impact or internal pressure. Therefore, the tensile strength and the elongation at break in each direction of the aluminum alloy foil are limited, and the obtained aluminum alloy foil is not easily deformed while having high formability. Further preferably, TD 45, tensile strength in at least one of MD directions is 90MPa or more, elongation at break is 12% or more, and 0.2% yield strength is 40MPa or more.

1.4.3 production of intermediate Metal layer 3

The surface wettability of the intermediate metal layer 3 is D or more, or the titration contact angle of distilled water is 15 or less, preferably 10 or less. If the wettability or surface water contact angle of the intermediate metal layer 3 is out of the given range, it is indicated that the possibility of rolling oil remaining on the metal in the production stage is high, and therefore the interfacial adhesion ability formed between the first corrosion-resistant layer 6, the intermediate metal layer 3 and the internal heat-sealable resin layer 5 is deteriorated, and there is a risk of separation between the intermediate metal layer 3 and the internal heat-sealable resin layer 5 during long-term storage of the battery, and the battery leakage is likely to occur, and as a preventive measure therefor, in addition to the annealing treatment at 150 ℃ or higher, the degreasing by plasma, corona method or alkali solution is performed, and the alkali degreasing method is to dip the metal in an alkali solution at 50 to 65 ℃, wash it with deionized water for 2 times after a certain period of treatment, and then dry it to obtain the degreased intermediate metal layer 3.

1.5 "" the second corrosion-resistant layer 7 and the first corrosion-resistant layer 6 ""

The second corrosion-resistant layer 7 or the first corrosion-resistant layer 6 of the invention has the functions of preventing hydrogen fluoride generated by the reaction of electrolyte and moisture from corroding the surface of the intermediate metal layer 3, preventing the separation and delamination of the intermediate metal layer 3, the outer substrate resin layer 1 and the inner heat-sealing resin layer 5, keeping the uniformity of the surface of the intermediate metal layer 3 and ensuring small change of adhesion and wettability in the packaging material for the lithium ion battery element.

The second corrosion-resistant layer 7 of the present invention is at least a single layer or a plurality of layers formed by coating or laminating a corrosion-resistant liquid or resin on the side of the intermediate metal layer 3 adjacent to the outer base resin layer 1.

The first corrosion-resistant layer 6 of the present invention is a single layer or a plurality of layers formed by coating or laminating at least a corrosion-resistant liquid or resin on the side of the intermediate metal layer 3 adjacent to the internal heat-sealing resin layer 5.

The thickness of the second corrosion-resistant layer 7 or the first corrosion-resistant layer 6 is not particularly limited, but is preferably 1nm to 3.0 μm, and more preferably 1nm to 1.5 μm from the viewpoint of the interlayer adhesion force between the intermediate metal layer and the hot-melt resin. In addition, the amount of the chromium in the anti-corrosion layer ranges from 8mg per square meter to 50mg per square meter, preferably from 10mg per square meter to 30mg per square meter.

1.5.1 fabrication of the second Corrosion resistant layer 7 with the first Corrosion resistant layer 6

Formation as the second corrosion-resistant layer 7 or the first corrosion-resistant layer 6 may be in a conventional manner in the art, for example: the first step is as follows: degreasing the surface of the internal thermal adhesive resin layer 8 or the external base resin layer 1 adjacent to or in contact with the intermediate metal layer 3 by a treatment method such as an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an oxygen activation method, or a heat treatment (annealing treatment) for calendering; the second step is that: the anti-corrosion liquid is used for coating by a bar coating method, a roll coating method, a gravure coating method, a dipping method and the like, a high-temperature chemical combination reaction acts on the surface of the intermediate metal layer 3, and the intermediate metal layer 3 coated with the anti-corrosion liquid is subjected to heat treatment at the high temperature of 130-.

1.5.2 composition of the second Corrosion resistant layer 7 and the first Corrosion resistant layer 6

Alternatively, the present invention emphasizes that the first corrosion-resistant layer 6 used includes a trivalent chromium compound, an inorganic acid, a fluoride, an organic resin, and water, and the proportions of the trivalent chromium compound, the inorganic acid, the fluoride, and the organic resin are (19-60): (3-60): (0-10): (6-60); wherein the ratio of the trivalent chromium compound to the organic resin is in the range of (3-100): 10. Wherein, the trivalent chromium compound in the first corrosion-resistant layer 6 at least comprises one of chromium nitrate, chromium phosphate, chromium fluoride and chromium chloride; the inorganic acid is at least one of nitric acid and phosphoric acid; examples of the fluoride include hydrofluoric acid, chromium fluoride, magnesium fluoride, an iron fluoride element, cobalt fluoride, nickel fluoride, ammonium fluoride, titanium fluoride and a complex thereof, zirconium fluoride salt or a complex thereof, magnesium fluoride, ammonium bifluoride, and the like, with chromium fluoride being preferred; the organic resin is composed of polyacrylic resin and polyvinyl alcohol, wherein the polyacrylic resin is one or more of polyacrylic acid, acrylic acid methacrylate copolymer, acrylic acid maleic acid copolymer, vinyl acetate styrene copolymer, polymethyl acrylate, copolymer of acrylic acid and maleic acid, copolymer of acrylic acid and styrene and sodium salt, ammonium salt and other derivatives thereof, preferably ammonium salt, sodium salt or amine salt and other derivatives of polyacrylic acid, more preferably copolymer of acrylic acid and dicarboxylic acid or dicarboxylic anhydride, and further preferably ammonium salt, sodium salt or amine salt of copolymer of acrylic acid and carboxylic acid or dicarboxylic anhydride; the weight average molecular weight of the polypropylene-based resin is limited to 1000 or more to maintain high durability, 100 ten thousand or less to maintain good production stability, and more preferably about 3000 to 80 ten thousand, because the higher the molecular weight, the higher the corrosion resistance, but the lower the water solubility of the polypropylene-based resin, the less stable the corrosion protection solution to be formulated, the less stable the production, and the lower the molecular weight, the lower the corrosion resistance.

Alternatively, the invention emphasizes that the first corrosion-resistant layer 6 at least comprises an aqueous solution composed of trivalent chromium compounds, inorganic acid, organic resin, organic solvent and titanate, and the proportion of the trivalent chromium compounds, the inorganic acid, the organic resin and the titanate in the first corrosion-resistant layer 6 is (25-38): (1-8): (10-12): (0-5). Wherein, the proportion of the trivalent chromium compound to the organic resin is controlled to be (2-4): 1 in the range of; the trivalent chromium compound in the first corrosion-resistant layer 6 is at least one of chromium nitrate, chromium fluoride, chromium chloride and chromium phosphate; the inorganic acid is at least one of nitric acid and hydrofluoric acid; the organic resin is polyvinyl alcohol; the titanate is not particularly limited, and may be selected from one or more of titanium sulfite, titanium oxysulfate, titanium ammonium sulfate, titanium nitrate, titanium ammonium nitrate, titanium sulfate, fluorotitanic acid and a complex thereof, ethyl acetoacetate, trimethylethanol, melamine, and n-butylhydroquinone.

Alternatively, the present invention emphasizes that the first corrosion-resistant layer 6 used is composed of at least a resin containing an aminated phenol polymer, a trivalent chromium compound, and a phosphorus compound, and the proportion of the aminated phenol polymer, the trivalent chromium compound, and the phosphorus compound in the first corrosion-resistant layer 6 is 1m per unit²In the resin film layer, the aminated phenol polymer is about 1 to 200mg, the trivalent chromium compound is about 0.5 to 50mg in terms of chromium and the phosphorus compound is about 0.5 to 50mg in terms of phosphorus.

Alternatively, the invention emphasizes the use of a first corrosion-resistant layer 6 comprising at least a first layer, close to the intermediate metal layer 3, of cerium oxide combined with a phosphoric inorganic substance, and, superimposed on the first layer 1, a second layer of at least a cationic or anionic polymer; wherein the inorganic phosphate includes phosphoric acid or a phosphate, and the inorganic phosphate is added to the layer 1 in an amount of 1 to 100 parts by mass per 100 parts by mass of cerium oxide.

The composition selection range of the second corrosion-resistant layer 7 is the same as that of the first corrosion-resistant layer 6.

1.6 "" first adhesive layer 4 ""

The first adhesive layer 4 is an intermediate layer provided to strongly bond the intermediate metal layer 3 and the internal heat-fusible resin layer 5, and the first adhesive layer 4 may be a single layer or a multilayer laminate.

The thickness of the first adhesive layer 4 is not particularly limited as long as it functions as an adhesive layer, and is preferably about 1 to 80 μm, and more preferably about 1 to 50 μm.

1.6.1 Components of the first adhesive layer 4

The composition of the first adhesive layer 4 at least comprises one or more of modified polyolefin resin, solution type adhesive and melting type adhesive.

1.6.1.1 modified polyolefin resin

Alternatively, the first adhesive layer 4 may contain at least a modified polyolefin resin, and examples of the modified polyolefin resin include a carboxylic acid-modified polyolefin, a carboxylic acid-modified cyclic polyolefin, a methacrylic acid-modified polyolefin, a maleic acid-modified polyolefin, an anhydrous maleic anhydride-modified polyolefin, a polyamide-modified polyolefin, an acrylic acid-modified polyolefin, a crotonic acid-modified polyolefin, and an imide-modified polyolefin; among them, acrylic acid-modified polyolefins, methacrylic acid-modified polyolefins, maleic acid-modified polyolefins, anhydrous maleic anhydride-modified polyolefins, and polyamide-modified polyolefins are preferable from the viewpoint of improving the adhesion between the intermediate metal layer 3 and the internal heat-fusible resin layer 5. In particular, the polyolefin and its modified resin used in the first adhesive layer 4 may be selected from the same types of resins as those used in the internal heat-sealing resin layer 5.

Optionally, the main component of the first adhesive layer 4 in the present invention is a modified polyolefin resin, wherein the polyolefin resin is a single layer or two or more layers formed by a mixture of one or more of a block copolymer polypropylene resin (B-PP), a random copolymer polypropylene resin (R-PP), and a homo-polypropylene resin (H-PP) containing polypropylene (PP) of more than 50%.

1.6.1.2 solution type inner layer adhesive

Optionally, from the viewpoint of stability of the packaging material for lithium ion battery elements in long-term use, the first adhesive layer 4 includes at least a solution-type adhesive, wherein a solute of the solution-type adhesive includes an acid-modified polyolefin resin as a main agent and one or more curing agents such as epoxy, polyfunctional isocyanate, carbodiimide, and oxazoline, and/or a curing agent combined with an amino compound such as triethylamine and N, N-dimethylethanolamine, and the solute of the solution-type adhesive may be at least one or more combinations of water, ethanol, isopropanol, ethyl acetate, methyl ethyl ketone, toluene, and methylcyclohexane. The acid value of the solution type adhesive is particularly limited in the present invention, and the acid value of the solution type adhesive is limited within the range of 0.5 to 200mg KOH/g, since the curing reaction point with the curing agent is small, the adhesion between the intermediate metal layer 3 and the internal heat-fusible resin layer 5 is unstable, and when the acid value of the solution type adhesive exceeds 200mg KOH/g, the curing reaction between the curing agent and the acid-modified polyolefin resin is too severe, a hard resin layer is formed, the bending resistance is deteriorated, the flexibility of the gold-plastic composite film is reduced, or cracks are generated due to bending, and the intermediate metal layer 3 and the internal heat-fusible resin layer 5 are peeled off.

Optionally, the method is carried out under the condition that no curing agent is arranged in the solution type adhesive: the solution type adhesive mainly comprises acid modified polyolefin and amine compound as hardening agents; the ratio of acid-modified polyolefin to amine compound is 10:1 to 125: 1, preferably 15:1 to 50: 1; wherein the acid-modified polyolefin resin is polypropylene having a melting point of 110 ℃ or higher, and the content of polypropylene is 50% or higher.

Wherein, the acid modifier used for the acid modified polyolefin resin used for the solution type adhesive is any one or combination of maleic anhydride, methacrylic acid, acrylic acid and itaconic anhydride, and the acid modifier is preferably maleic anhydride or acrylic acid modified polyolefin; the melting point of the polyolefin resin in the acid-modified polyolefin resin is particularly limited, and the melting point is preferably 60-155 ℃ because the intermediate metal layer 3 and the internal heat-fusible resin layer 5 are peeled off at a high temperature when the melting point is below 60 ℃, and the heat resistance is better when the melting point exceeds 155 ℃, but when the melting point is reacted with a curing agent, a hard resin layer is formed, the flexibility is not good, the gold-plastic composite film is reduced, cracks are generated during bending, and the intermediate metal layer 3 and the internal heat-fusible resin layer are peeled off 8; the weight average molecular weight of the polyolefin resin in the acid-modified polyolefin resin is particularly limited in the present invention, and it is emphasized that the weight average molecular weight is preferably in the range of 10000-150000 because the resin has high fluidity when heated and becomes thin significantly when heat-sealed, the adhesion strength between the intermediate metal layer 3 and the internal heat-fusible resin layer 5 (in the case of the reaction of adding a curing agent) becomes low, and there is a problem of sealability, and if the weight average molecular weight exceeds 150000, the intermediate metal layer 3 and the internal heat-fusible resin layer 5 (in the case of the reaction of adding a curing agent) form a hard resin layer, the bending resistance is deteriorated, the flexibility of the gold-plastic composite film 5 is reduced, or cracks are generated by bending, and the intermediate metal layer 3 and the internal heat-fusible resin layer 5 are peeled off.

The epoxy curing agent used for the solution-type adhesive is not particularly limited as long as it is a compound having at least 1 epoxy group, and examples thereof include epoxy resins such as bisphenol a diglycidyl ether, modified bisphenol a diglycidyl ether, novolac glycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether; the polyfunctional isocyanate-based curing agent to be used is not particularly limited as long as it is a compound having 2 or more isocyanate groups in the molecule, and for example, a component obtained by polymerization or addition of isophorone diisocyanate (PDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or the like, or a reaction product of such a mixture with another polymer; the carbodiimide-based curing agent used is not particularly limited as long as it is a compound having at least 1 carbodiimide group (-N ═ C ═ N-) in the molecule, and a polycarbodiimide compound having at least 2 or more carbodiimide groups is preferred; the oxazoline-based curing agent to be used is not particularly limited as long as it is a compound having an oxazoline skeleton.

In terms of production, the solution-type adhesive made of the solute and the solvent may be applied to the first corrosion-resistant layer 6 for adhering the intermediate metal layer 3 and the internally heat-fusible resin layer 5, and the solvent is evaporated by heating to obtain the first adhesive layer 4 having a thickness of 1 to 50 μm, preferably about 1 to 10 μm, more preferably 1 to 5 μm, and in the case where the thickness is less than 1 μm, the thickness is too thin, so that the adhesion between the intermediate metal layer 3 and the internally heat-fusible resin layer 5 is lowered and the adhesion becomes a problem; when the thickness exceeds 10 μm, adhesion is ensured, but when the curing agent reacts, a hard resin layer is formed, the bending resistance is deteriorated, flexibility of the outer package for a battery element is lowered, there is a risk of cracking due to bending, and there is an increased risk of peeling the intermediate metal layer 3 and the internal heat-sealing resin layer 5.

1.6.1.3 fusion-type inner layer adhesive

Alternatively, the composition of the first adhesive layer 4 includes at least a melt type adhesive whose component contains an acid-modified polyolefin resin, and preferably, the thickness of the first adhesive layer 4 is 5 to 50 μm.

Among them, the present invention has a specific limitation on the melting point of the acid-modified polyolefin resin used for the melt type adhesive, and has a problem of sealability because the fluidity of the resin is high when the melting point of the acid-modified polyolefin resin is 135 ℃ or lower due to heating, the thickness becomes thin seriously when heat sealing is performed under pressure, the adhesion strength between the intermediate metal layer 3 and the inner heat-fusible resin layer 5 is lowered, and the fluidity is relatively low when heat sealing is performed under pressure and the heat resistance is improved when the melting point is 165 ℃ or higher, but when the acid-modified polyolefin resin is compounded with the intermediate metal layer 3, the heat shrinkage amount is increased to increase the internal stress, the adhesion ability between the heat-fusible inner layer 8 and the intermediate metal layer 3 is lowered, and therefore, if the resin is stored for a long period of time, the resin may be peeled from the intermediate metal layer 3, and further heat shrinkage may occur due to heating at the time of heat sealing, and the adhesion between the intermediate metal layer 5 is lowered, the sealing strength becomes low and the sealing performance is seriously influenced, so that the melting point of the acid modified polyolefin resin is specially limited to 135-165 ℃; meanwhile, the present invention has a specific limitation on the MFR (230 ℃) value of the acid-modified polyolefin resin used in the melt type adhesive, and the present invention has a specific limitation on the MFR (230 ℃) value of the acid-modified polyolefin resin, because when the MFR (230 ℃) of the acid-modified polyolefin resin is less than 3g/10min, and the acid-modified polyolefin resin is extruded onto the intermediate metal layer after heat-melting and compounded, the extrusion film forming property is liable to be unstable, and if the MFR (230 ℃) of the acid-modified polyolefin resin is more than 15g/10min, the resin fluidity is increased by heating, and the adhesion strength of the intermediate metal layer 3 and the inner heat-sealable resin layer 5 is lowered by severe thinning at the time of heat-sealing under pressure, and there is a problem of sealability, so that the present invention specifically limits the MFR (230 ℃) of the acid-modified polyolefin resin to 3 to 10g/10 min; further, the present invention is particularly limited in the degree of modification of the acid-modified polyolefin resin used for the melt type adhesive, and it is preferable to avoid such a phenomenon because when the degree of modification of the hot-melt type first adhesive layer 4 is less than 1%, the adhesion to the intermediate metal layer 3 becomes unstable, and when the degree of modification exceeds 15%, the physical property problem does not occur, but the production price increases, and therefore, the present invention is particularly limited to the degree of modification of the polyolefin resin used in the range of 1% to 15%, preferably 3% to 12%. Specifically, the acid-modified polyolefin resin used in the melt adhesive is any of modified polyolefin resins such as maleic anhydride, methacrylic acid, acrylic acid, and itaconic anhydride.

1.7 "" internal heat-sealing resin layer 5 "

In the exterior material for a battery element of the present invention, which is highly formable and excellent in durability, the inner heat-fusible resin layer 5 is a layer in which the battery element is sealed by heat-fusing the heat-fusible resin layers to each other at the time of assembling the battery, and may also be referred to as a heat-seal layer, and the inner heat-fusible resin layer 5 of the present invention may be formed by laminating a single layer or a plurality of layers of the same or different resin layers.

The thickness of the inner heat-fusible resin layer 5 is not particularly limited as long as the function of sealing the battery element is exerted after the heat-fusible resin layers are heat-fused to each other, and may be about 100 μm or less, more preferably about 25 to 80 μm.

1.7.1 composition of the layer of thermally weldable resin 5

The resin constituting the internal heat-fusible resin layer is not particularly limited, and is mainly heat-fusible, and a resin having a polyolefin main chain such as polyolefin and acid-modified polyolefin is preferable.

1.1.7.1 polyolefin

Specific examples of the polyolefin include polypropylene such as polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, ethylene- α -olefin copolymers, homopolypropylene, polypropylene block copolymers (for example, a block copolymer of propylene and ethylene), and random copolymers of polypropylene (for example, a random copolymer of propylene and ethylene); propylene- α -olefin copolymers; ethylene-butene-propylene terpolymers, and the like; among them, polypropylene is preferable. The polyolefin resin in the case of the copolymer may be a block copolymer or a random copolymer.

1.1.7.2 acid-modified polyolefin resin

The acid-modified polyolefin resin is a polymer modified by block polymerization or graft polymerization of a polyolefin with an acid component, and may be a copolymer obtained by copolymerization of a polar molecule such as polyacrylic acid or methacrylic acid with a polyolefin; among them, carboxylic acids or sulfonic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, and anhydrides thereof can be used as the acid component, and acrylic acid or maleic acid and anhydrides thereof are preferably used.

Alternatively, the internal heat-sealing resin layer 5 may be a composite film formed of one or more layers of at least two polymers selected from acid-modified polyolefin resin, homo-polypropylene, block co-polypropylene, random co-polypropylene, and polyethylene.

Preferably, the melting point of the constituent resin of the heat-fusible resin layer 5 of the present invention is limited based on the fact that when the melting point of the constituent resin is 120 ℃ or less, the fluidity at the time of heating is high, when heat-sealing under pressure is performed, the thickness becomes thin, the adhesion force with the intermediate metal layer 3 is decreased, the resin flows to the edge portion not pressed by the pressing at the pressed portion inside the battery, the expansion and shrinkage of the battery and the external force of the bending process cause cracks, the electrolyte penetrates to the intermediate metal layer through the cracks, the insulation resistance of the heat-fusible resin layer is decreased, the leakage phenomenon occurs, the battery life is shortened, when the melting point exceeds 162 ℃, the crystallinity of the resin is increased, the fluidity at the heat-sealing under pressure is relatively lowered, the heat resistance is improved, but when the high crystalline resin is heat-sealed, a hard and brittle resin layer is formed, and therefore, when the external force of the expansion and shrinkage of the bending process of the battery, etc., the resin layer is easy to crack, and the long-term stable sealing performance cannot be obtained, so the melting point of the resin composing the internal heat welding resin layer 5 is preferably 120-162 ℃, and more preferably 130-162 ℃; the MFR (230 ℃) of the resin constituting the heat-fusible resin layer 5 of the present invention is limited based on the fact that when the MFR (230 ℃) of the resin is less than 2g/10min, the fluidity of the resin at the time of heat sealing under pressure is low, and stable sealing properties are hardly obtained, and when the MFR (230 ℃) of the resin exceeds 15g/10min, the fluidity of the resin at the time of heat sealing under pressure is too high, the thickness of the resin becomes very thin, and stable sealing properties are hardly obtained, and further, the resin flows to the edge portion not pressed by the pressing in the pressed portion inside the battery, and cracks are caused by external force of expansion and contraction of the battery, and the electrolyte penetrates into the intermediate metal layer through the cracks, causing a decrease in insulation resistance of the heat-fusible resin layer, a leakage phenomenon occurs, and the battery life is shortened, and therefore, it is preferable that the MFR (230 ℃) of the resin constituting the heat-fusible resin layer 5 is 2 to 15g/10min, more preferably, the MFR (230 ℃) is 3 to 12g/10 min; the present invention limits the thickness of the inner heat-fusible resin layer 5, and based on the fact that when the thickness of the inner heat-fusible resin layer is less than 20 μm, the thickness cannot sufficiently cover the variation of the machining dimension and the variation of the condition of a heat sealing device or the like, it is difficult to obtain a uniform heat-fused portion, and further stable sealing property cannot be obtained,

in addition, the resin flows to the non-pressed edge part by pressing, the thickness of the internal heat-sealing resin layer becomes thin, the expansion and contraction of the battery and the external force of bending processing are easy to cause cracks, the electrolyte penetrates to the middle metal layer through the cracks, the insulation resistance of the internal heat-sealing resin layer is reduced, the electric leakage phenomenon occurs, and the service life of the battery is shortened. When the thickness of the internal heat-sealing resin layer exceeds 120 μm, the water vapor transmission amount is increased, the moisture in the battery is increased, gas is generated by reaction with the electrolyte, the danger of expansion, rupture and liquid leakage is easy to occur, the battery life is reduced, the metal layer subjected to corrosion prevention treatment is corroded by excessive hydrogen fluoride, the adhesion strength between the intermediate metal layer and the internal heat-sealing resin layer is reduced, the electrolyte leakage is easy to occur, and the like, so that the internal heat-sealing resin layer 5 consisting of one or more resin films is preferably 20 to 120 μm, more preferably 25 to 80 μm; when the inner heat-fusible resin layer 5 is a multilayer, the side contacting the intermediate metal layer 3 is an inner resin layer, and the side away from the intermediate metal layer 3 is an outer resin layer, preferably, the outer resin layer has a thickness of 2 μm or more and a melting point of 130-152 ℃.

To produce, the internal heat-weldable resin layer 5 is laminated to the intermediate metal layer 3 by hot extrusion to form one or more internal heat-weldable resin layers 5.

Regarding the production, the internal heat-sealable resin layer 5 can be laminated to the intermediate metal layer 3 by means of the first adhesive layer 4, in which case a heat treatment at 60 ℃ below the melting point of the first adhesive layer 4 is carried out.

1.1.7.3 aid

In order to improve the moldability of the exterior material for battery elements, which is highly moldable and excellent in durability, the internal heat-fusible resin layer may contain a slip agent as needed, the type of slip agent is not particularly limited and may be selected from a known range, one slip agent may be used alone or two or more slip agents may be used in combination, the slip agent may be exuded from the resin constituting the internal heat-fusible resin layer 5 or may be applied to the surface of the internal heat-fusible resin layer 5; an amide-based slipping agent is preferably used, and the amide-based slipping agent is preferably used on the surface layer of the outer base resin layer 7; the content of slipping agent is preferably 10-50mg/m²More preferably 15 to 40mg/m²。

The inner heat-sealable resin layer 5 may contain an antioxidant or other component as needed to suppress thermal deterioration in the production process, and the type of antioxidant is not particularly limited and may be selected from known ranges, and 1 antioxidant may be used alone or 2 or more antioxidants may be used in combination.

2. Preparation of high-forming gold-plastic composite film

Based on the foregoing description of the laminated structures that the composite gold-plastic film may comprise, the following lists several possible ways of laminating the laminated structures of the composite gold-plastic film of the present invention:

2.1 deoiling treatment of the intermediate Metal layer 3

The surface wettability of the intermediate metal layer 3 is 65mN/m, preferably 70mN/m or more, or the titration contact angle of distilled water is 15 degrees or less, preferably 10 degrees or less. If the wettability or surface water contact angle of the intermediate metal layer 3 is out of the given range, it is indicated that the possibility of the rolling oil remaining on the metal in the production stage is high, and therefore the interface adhesion capability formed between the intermediate metal layer 3 and the internal heat-sealing resin layer 5 of the

anti-corrosion layer

6 or 7 is deteriorated, and the interface adhesion capability formed between the intermediate metal layer 3 and the internal heat-sealing resin layer 5 is deteriorated, and the risk of separation between the intermediate metal layer 3 and the internal heat-sealing resin layer 5 during long-term storage of the battery is high, and the battery leakage is likely to occur, and as a preventive measure thereof, the annealing treatment at 150 ℃ or higher can be performed, and the degreasing by the plasma, corona method, or alkali method is performed by immersing the metal in an alkali solution at 50 to 65 ℃ and washing with deionized water for 2 times after a certain period of treatment, followed by drying, to obtain the degreased metal.

2.2 formation of the

Corrosion protection layer

6 or 7 on the intermediate Metal layer 3

After applying an anticorrosive solution to the surface of the intermediate metal layer 3 on the side in contact with the internal heat-fusible resin layer 5, the intermediate metal layer is heat-treated at a high temperature for a certain period of time.

2.3 lamination between the outer substrate resin layer 1 and the intermediate metal layer 3

Coating polyurethane adhesive dissolved by organic solvent between the middle metal layer 3 and the outer base material resin layer 1, heating for a certain time at a certain temperature to volatilize the organic solvent to form a second adhesive layer 2, further compounding the outer base material resin layer 1, the second adhesive layer 2 and the middle metal layer 3 at a certain temperature and pressure, storing for a certain time at a certain temperature, and then carrying out curing reaction on the second adhesive layer 2 to obtain the composite resin layer consisting of the outer base material resin layer 1, the second adhesive layer 2 and the middle metal layer 3. When the outer-layer adhesive is not used for compounding the outer-base-material resin layer 1 and the intermediate metal layer 3, the intermediate metal layer 3 and the outer-base-material resin layer 1 are compounded in a heating and pressurizing mode, and the outer-base-material resin layer 1 is processed by heating, ultraviolet treatment and electronic wires to be filmed, so that the composite resin layer consisting of the outer-base-material resin layer 1 and the intermediate metal layer 3 can be obtained.

As is apparent from the above, there may also be a coloring layer 8, a second corrosion-resistant layer 7, a first corrosion-resistant layer 6, a coloring layer 8, a second corrosion-resistant layer 7, a composite manner of the first corrosion-resistant layer 6 and the intermediate metal layer 3 between the intermediate metal layer 3 and the outer substrate resin layer 1, and the description can be made with reference to the production of the coloring layer 8, 1.3.1, the production of the second corrosion-resistant layer 7, and the first corrosion-resistant layer 6.

2.4 lamination between the intermediate metal layer 3 and the internally heat-sealable resin layer 5

After obtaining the composite resin layer composed of the outer substrate resin 1 and the intermediate metal layer 3, the intermediate metal layer 3 and the internal heat-sealing resin layer 5 can be composited in any mode;

a. dry compounding method: the solution type inner layer adhesive composed of a main agent, a curing agent and an organic solvent is coated on the anti-corrosion surface of the middle metal layer 3 of the composite film composed of the outer base material resin layer 1 and the middle metal layer 3, the solution type inner layer adhesive is dried to form a first adhesive layer 4, the first adhesive layer 4 is thermally compounded with the bonding surface of the inner heat-sealing resin layer 5 under certain temperature and pressure, and then curing treatment is carried out, so that a composite product of the outer base material resin layer 1/the second adhesive layer 2/the middle metal layer 3/the first adhesive layer 4/the inner heat-sealing resin layer 5 is formed. Preferably, the adhesive surface of the internally heat-fusible resin layer 5 in contact with the first adhesive layer 4 is subjected to corona treatment in advance. In addition, a curing treatment at a temperature of 60 ℃ or less, which does not exceed the melting point of the first adhesive layer 4, may be performed.

b. Melt extrusion method: the first adhesive layer 4 containing a melt adhesive is formed on the intermediate metal layer 3 or the first corrosion-resistant layer 6 of the intermediate metal layer 3 by melt extrusion, and the surface of the first adhesive layer 4 is thermally compounded with the bonding surface of the internal heat-sealing resin layer 5 to form a composite product comprising the outer substrate resin layer 1/the second adhesive layer 2/the intermediate metal layer 3 (or the second corrosion-resistant layer 7/the intermediate metal layer 3/the first corrosion-resistant layer 6)/the first adhesive layer 4/the internal heat-sealing resin layer 5, and in order to improve the peeling force between the intermediate metal layer 3 and the internal heat-sealing resin layer 5, heat treatment at a temperature of 60 ℃ or less than the melting point temperature of the first adhesive layer 4 can be performed.

c. Co-melt extrusion method: the first adhesive layer 4 and the internal heat-sealing resin layer 5, which contain melting type adhesives, form a composite product of the outer substrate resin layer 1/the second adhesive layer 2/the intermediate metal layer 3 (or the second corrosion-resistant layer 7/the intermediate metal layer 3/the first corrosion-resistant layer 6)/the first adhesive layer 4/the internal heat-sealing resin layer 5 by a co-extrusion method, if the surface of the intermediate metal layer 3 contacted with the first adhesive layer 4 is subjected to corrosion protection, in order to improve the peeling force between the intermediate metal layer 3 and the internal heat-sealing resin layer 5, the heat treatment can be carried out at a temperature of 60 ℃ below the melting point of the first adhesive layer 4.

d. The heat bonding method comprises dissolving a resin main agent having a melting point of 100 ℃ or higher and a curing agent in an aqueous or organic solvent to form a solution-type inner layer adhesive. The coating solution is applied to the metal layer anticorrosive treated surface 6 of the composite layer composed of the outer base resin layer 1 and the intermediate metal 3 layer, and the solution type inner layer adhesive is dried to form the first adhesive layer 4. And thermally compounding the adhesive surface of the inner heat-sealing resin layer 5 at a certain temperature and pressure to form a composite product of the outer base material resin layer 1, the second adhesive layer 2, the middle metal layer 3, the first adhesive layer 4 and the inner heat-sealing resin layer 5. In order to increase the peel force between the intermediate metal layer 3 and the internally heat-fusible resin layer 5, a heat treatment may be performed at a temperature of 60 c not exceeding the melting point of the first adhesive layer 4. The inner heat-sealable resin layer 5 may be formed by extrusion, or a film may be used, and when a film is used, it is preferable that the adhesive surface of the inner heat-sealable resin layer 5 in contact with the first adhesive layer 4 is subjected to corona treatment in advance.

3. Test mode of high-forming gold-plastic composite film

3.1 outer substrate resin layer (i.e. laminate in the independent claim of the invention) 1 multilayer Co-extruded Structure between layers a and c Peel strength

The outer base resin layer 1 was prepared in a straight strip shape with a sample size of 100 x 15mm, the peeling test between the a layer and the c layer in the outer base resin layer 1 was performed using a tensile test apparatus, the peeled a layer film was placed in an upper plate of a stretching test apparatus, the c layer film was placed in a lower plate, and then, T-peeling was performed with a peeling surface of 180 ° at a stretching speed of 50mm/min, and the peeling strength between the a layer and the c layer was measured. The peel strength was read in such a manner that the moving distance of the a-layer and the c-layer was 50mm, and the average value of the peel strength between the moving distances of 10mm and 40 mm was selected. 5/group were tested in parallel.

3.2 puncture Strength of outer base resin layer (i.e., laminate in the independent claim of the present invention) 1 or highly molded gold-plastic composite film Degree of rotation

According to the JIS Z1707 standard, the puncture speed was 50mm/min, the needle diameter was 1.0mm, and the radius of the tip shape was 0.5mm, as shown below. The maximum value of the puncture through the film was taken as the puncture strength.

3.3 outer base resin layer (i.e. laminate in the independent claim of the invention) 1 or highly formed gold-plastic composite filmAccording to JIS C2110 standard, an electrode is formed in air at 23 ℃ or 40 ℃ by a short time method

Cylinder/Φ 75 cylinder, insulation breakdown voltage was measured by an insulation breakdown tester having a maximum voltage of 100kV under the condition of 0.3 kV/sec.

3.4 Forming depth

The molding size is 98mm multiplied by 57mm, the pressing pressure is 1.0MPa, the corner r is 1.0mm, the angle r of the convex side is 1.0mm, and the gap between the convex side and the concave side is 0.5 mm.

The following will exemplify a manufacturing manner in which a gold-plastic composite film provided with an outer substrate resin layer 1/a second adhesive layer 2/a second corrosion-resistant layer 7/an intermediate metal layer 3/a first corrosion-resistant layer 6/a first adhesive layer 4/an internal heat-seal resin layer 5 is sequentially laminated as shown in fig. 4.

The lamination method is as follows: a resin layer 1 and a second adhesive layer on the outer substrate in advance2The contacting surfaces are corona treated. An aluminum alloy foil layer 3 is laminated by a dry lamination method using an outer base resin layer 1 of a multi-layer co-extrusion structure having at least a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer) 3 layer of the present invention. Specifically, a passivation solution was applied to both sides of a 40 μ aluminum alloy foil 3 having a surface contact angle of 15 after annealing and degreasing to form a first corrosion-resistant layer 6 and a second corrosion-resistant layer7Mixing amorphous polyester polyol with the weight-average molecular weight of 5000, Tg of 50 ℃ and the hydroxyl value of 25mg KOH/g and amorphous polyester polyol with the weight-average molecular weight of 20000, Tg of-17 ℃ and the hydroxyl value of 8mg KOH/g according to the weight ratio of 3:2, adding Toluene Diisocyanate (TDI) to form mixed outer-layer bonding liquid with the NCO/OH ratio of 6.2, and coating the matte surface of the aluminum alloy foil 3 to form a second adhesive layer 2(3 mu m). The second adhesive layer 2 and the outer base resin are laminatedAfter the layer 1 is compounded, curing treatment is carried out for 3 days at the temperature of 80 ℃ to prepare an outer base material resin layer 1/a second adhesive layer 2/a second corrosion-resistant layer 7/an aluminum alloy foil 3. Hereinafter, outer base resin layer 1/second adhesive layer2/Second corrosion resistant layer7/Aluminum alloy foil3As a composite outer matrix resin composite film.

A first corrosion-resistant layer 6 and a second corrosion-resistant layer7The anti-corrosion coating is mainly an aqueous solution consisting of chromium nitrate, phosphoric acid, nitric acid and polyacrylic acid (PAA), wherein the proportion of the chromium nitrate, the phosphoric acid, the nitric acid and the polyacrylic acid (PAA) in the

anti-corrosion layer

6 or 7 coated on the aluminum alloy foil layer 3 is controlled to be 58: 4: 0.7: 5 the chromium content is 15mg per square meter.

The method of lamination between the intermediate metal layer 3 and the internally heat-sealable resin layer 5 can be selected from the above "2.4 intermediate metal layer 3 and inner Composite of thermal fusion-bonded resin layers 5 "a. b, c and d.

Example 1

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c and 3 layers, wherein the layer a is PET, the layer b is a 2-layer structure formed by thermal co-extrusion of acid modified polyolefin and sulfopolyester, the layer thickness ratio of the acid modified polyolefin to the sulfopolyester is 1:1, the thickness of the layer b is 2 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.23 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.16 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.4N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 2.1N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.67N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The intermediate metal layer 3 is a 30 μm heat-treated austenitic stainless steel foil, both surfaces of which are subjected to an anti-corrosion treatment with an anti-corrosion solution.

The second adhesive layer 2 used for compounding the outer substrate resin layer 1 and the middle metal layer 3 is as follows: a main agent obtained by mixing a non-crystalline polyester polyol having a weight average molecular weight of 5000, a Tg of 50 ℃ and a hydroxyl value of 25mgOH/g with a non-crystalline polyester polyol having a weight average molecular weight of 20000, a Tg of-17 ℃ and a hydroxyl value of 8mgOH/g in a weight ratio of 3:2 was added with a Toluene Diisocyanate (TDI) curing agent, and the mixture was mixed to form a second adhesive layer 2 having a thickness of 3 μm.

The outer substrate resin layer 1/the second adhesive layer 2/the second corrosion-resistant layer 7/the intermediate metal layer 3/the first corrosion-resistant layer 6/the first adhesive layer 4/the internal heat-seal resin layer 5, which are mentioned in the above-mentioned manufacturing method of the gold-plastic composite film in which the outer substrate resin layer 1/the second adhesive layer 2/the second corrosion-resistant layer 7/the aluminum alloy foil 3 are sequentially laminated, are used as the composite mode of the outer substrate resin composite film between the outer substrate resin layer 1 and the intermediate metal layer 3.

The first adhesive layer 4 was compounded with the internal heat-sealing resin layer 5 in the manner of a, and the thickness of the internal heat-sealing resin layer 5 was 80 μm.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.12 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.18N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 4.5 mm.

Example 2

The outer base resin layer 1 is a co-extrusion structure with a layer a, a layer b and a layer c, the layer a is PET, the layer b is a two-layer structure formed by thermal co-extrusion of acid modified polyolefin and modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin to the modified polyester elastomer is 1:1, the layer b is 2 micrometers thick, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.25 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.18 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.3N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 2.0N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.66N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The intermediate metal layer is a 30 μm heat-treated austenitic stainless steel foil, both surfaces of which are subjected to an anti-corrosion treatment with an anti-corrosion solution.

The selection of the second adhesive layer 2 and the compounding manner between the outer base resin layer 1 and the intermediate metal layer 3 were the same as in example 1.

The first adhesive layer 4 is compounded with the internal heat-sealing resin layer 5 in a manner of d, and the thickness of the internal heat-sealing resin layer 5 is 80 μm.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.11 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.18N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 4.5 mm.

Example 3

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a three-layer structure of acid modified polyolefin/sulfopolyester/modified polyester elastomer formed by thermal co-extrusion of acid modified polyolefin, sulfopolyester and modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfopolyester/modified polyester elastomer is 2:1:2, the thickness of the layer b is 2 μm, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.24 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.17 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.5N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 2.3N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.67N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The intermediate metal layer 3 is a 30 μm heat-treated austenitic stainless steel foil, both surfaces of which are subjected to an anti-corrosion treatment with an anti-corrosion liquid.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.12 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was allowed to stand at 23 ℃ and 50% relative humidity for 24 hours, and then tested for puncture strength of 0.2N/. mu.m. In addition, the depth of the punch was 4.5 mm.

Example 4

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a two-layer structure formed by an acid modified polyolefin/modified polyester elastomer and a modified polyester elastomer blend formed by hot co-extrusion of a mixture of acid modified polyolefin, a sulfo-containing polyester and a modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfo-containing polyester and modified polyester elastomer blend is 1:1, the mixing ratio of the sulfo-containing polyester and the modified polyester elastomer is 1:3, the thickness of the layer b is 2 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and relative humidity of 50% for 24 hours, the breakdown voltage of the material is tested to be 0.26 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.17 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.5N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 1.9N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.68N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The first adhesive layer 4 was compounded with the internal heat-sealing resin layer 5 in the form of c, and the thickness of the internal heat-sealing resin layer 5 was 80 μm.

The outer base resin layer 1, the intermediate metal layer 3 and the internal heat-sealing resin layer 5 are laminated by the above method to form the high-formability gold-plastic composite film of the invention. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.12 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.19N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 4.5 mm.

Example 5

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c and 3 layers, wherein the layer a is PET, the layer b is composed of a mixture of sulfopolyester and a modified polyester elastomer, the mixing ratio of the sulfopolyester to the modified polyester elastomer is 1:1, the thickness of the layer b is 2 mu m, the layer c contains nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.25 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.18 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.5N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 2N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.66N/. mu.m after being left at 23 ℃ and a relative humidity of 50% for 24 hours.

The selection of the second adhesive layer 2 and the compounding of the outer base resin layer 1 and the intermediate metal layer 3 are the same as in example 1.

The first adhesive layer 4 was compounded with the internal heat-sealing resin layer 5 in the manner of b, and the thickness of the internal heat-sealing resin layer 5 was 80 μm.

The outer base resin layer 1, the intermediate metal layer 3 and the internal heat-sealing resin layer 5 are laminated by the above method to form the high-formability gold-plastic composite film of the invention. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.12 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for a puncture strength of 0.17N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 4.5 mm.

Example 6

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c and 3 layers, wherein the layer a is PET, the layer b is a two-layer co-extrusion structure formed by co-extruding the layer b-1 and the layer b-2 (wherein the layer b-2 is in contact with the layer c), the mixing ratio of the sulfopolyester and the modified polyester elastomer in the layer b-1 is 1:3, the mixing ratio of the sulfopolyester and the modified polyester elastomer in the layer b-2 is 3:1, the thickness of the layer b is 2 mu m, the layer c contains nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.23 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.16 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.2N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 2.2N/15mm under a test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.67N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.13 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was allowed to stand at 23 ℃ and 50% relative humidity for 24 hours, and then tested for puncture strength of 0.2N/. mu.m. In addition, the depth of the punch was 4.5 mm.

Example 7

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a two-layer structure formed by an acid modified polyolefin/modified polyester elastomer and a modified polyester elastomer blend formed by hot co-extrusion of a mixture of acid modified polyolefin, a sulfo-containing polyester and a modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfo-containing polyester and modified polyester elastomer blend is 1:1, the mixing ratio of the sulfo-containing polyester and the modified polyester elastomer is 1:3, the thickness of the layer b is 2 mu m, the layer c is aromatic polyamide MXD6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 by a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.25 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.16 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.2N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 2.2N/15mm under a test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.67N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The intermediate metal layer 3 is a 50 μm annealed nickel-plated iron foil having a 1 μm thick nickel layer plated on the surface thereof, and both sides of the nickel-plated iron foil are subjected to an anti-corrosion treatment with an anti-corrosion solution.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.11 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.27N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 6.0 mm.

Example 8

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a two-layer structure formed by an acid modified polyolefin/modified polyester elastomer and a modified polyester elastomer blend formed by hot co-extrusion of a mixture of acid modified polyolefin, a sulfo-containing polyester and a modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfo-containing polyester and modified polyester elastomer blend is 1:1, the mixing ratio of the sulfo-containing polyester and the modified polyester elastomer is 1:3, the thickness of the layer b is 2 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.26 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.15 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.2N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 1.9N/15mm under the test environment of 90 +/-2% at 40 ℃. Further, it was tested to have a puncture strength of 0.65N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The intermediate metal layer 3 is a 40 μm 8021-series annealed aluminum foil, both sides of which are subjected to an anti-corrosion treatment with an anti-corrosion solution.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.10 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was allowed to stand at 23 ℃ and 50% relative humidity for 24 hours, and then tested for puncture strength of 0.15N/. mu.m. In addition, the depth of the punch was 10.0 mm.

Example 9

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a two-layer structure formed by an acid modified polyolefin/modified polyester elastomer and a modified polyester elastomer blend formed by hot co-extrusion of a mixture of acid modified polyolefin, a sulfo-containing polyester and a modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfo-containing polyester and modified polyester elastomer blend is 1:1, the mixing ratio of the sulfo-containing polyester and the modified polyester elastomer is 1:3, the thickness of the layer b is 1 μm, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.24 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.15 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.0N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 1.7N/15mm under the test environment of 90 +/-2% at 40 ℃. Further, it was tested to have a puncture strength of 0.65N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.10 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.14N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 10.0 mm.

Example 10

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a two-layer structure formed by an acid modified polyolefin/modified polyester elastomer and a modified polyester elastomer blend formed by hot co-extrusion of a mixture of acid modified polyolefin, a sulfo-containing polyester and a modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfo-containing polyester and modified polyester elastomer blend is 1:1, the mixing ratio of the sulfo-containing polyester and the modified polyester elastomer is 1:3, the thickness of the layer b is 3 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and relative humidity of 50% for 24 hours, the breakdown voltage of the material is tested to be 0.26 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.15 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.2N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 1.7N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.66N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The first adhesive layer 4 was compounded with the internal heat-sealable resin layer 5 in the manner of c, and the thickness of the internal heat-sealable resin layer 5 was 80 μm.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.10 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.16N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 10.0 mm.

Example 11

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a three-layer structure of acid modified polyolefin/sulfopolyester/modified polyester elastomer formed by thermal co-extrusion of acid modified polyolefin, sulfopolyester and modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfopolyester/modified polyester elastomer is 2:1:2, the thickness of the layer b is 2 μm, the layer c is aromatic polyamide MXD6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.24 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.17 kv/mum. Secondly, the peel strength of the layer a/layer c is 3.5N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 2.3N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.67N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The outer base resin layer 1 thus formed was hot-press-laminated with the intermediate metal layer 3 at a temperature of 200 ℃ to form an annealed nickel-plated iron foil having a thickness of 1 μm on the surface of the intermediate metal layer 3, and the thickness of the nickel layer was 50 μm.

The internal heat welding resin layer 5 is compounded by casting two layers of molten coextrusion on the intermediate metal layer 3, acid modified polyolefin is added into the layer of internal heat welding resin layer which is in contact with the intermediate metal layer 3, and the thickness of the internal heat welding resin layer 5 is 80 mu m.

Comparative example 1

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a two-layer structure formed by an acid modified polyolefin/modified polyester elastomer and a modified polyester elastomer blend formed by hot co-extrusion of a mixture of acid modified polyolefin, a sulfo-containing polyester and a modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfo-containing polyester and modified polyester elastomer blend is 1:1, the mixing ratio of the sulfo-containing polyester and the modified polyester elastomer is 1:3, the thickness of the layer b is 5 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.26 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.02 kv/mum. Secondly, the peel strength of the layer a/layer c is 2.5N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.4N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.6N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.09 kv/mum after the high-molding gold-plastic composite film is placed at 23 ℃ and 50% of relative humidity for 24 h. Next, it was tested for puncture strength of 0.12N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 6.5 mm.

Comparative example 2

The outer base resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a two-layer structure formed by an acid modified polyolefin/modified polyester elastomer and a modified polyester elastomer blend formed by thermal co-extrusion of a mixture of acid modified polyolefin, a sulfopolyester and a modified polyester elastomer, the layer thickness ratio of the acid modified polyolefin/sulfopolyester and modified polyester elastomer blend is 1:1, the mixing ratio of the sulfopolyester and the modified polyester elastomer is 1:3, the thickness of the layer b is 0.5 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base resin layer 1 by a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.20 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.12 kv/mum. Secondly, the peel strength of the layer a/layer c is 2.0N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.8N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.55N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours.

The first adhesive layer 4 was compounded with an internally heat-sealable resin layer having a thickness of 80 μm in the manner of d.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.09 kv/mum after the high-molding gold-plastic composite film is placed at 23 ℃ and 50% of relative humidity for 24 h. Next, it was allowed to stand at 23 ℃ and 50% relative humidity for 24 hours, and then tested for puncture strength of 0.1N/. mu.m. In addition, the depth of the punch was 7.5 mm.

Compared with the example 8, although the PET/PA co-extrusion film with a new structure is adopted in the comparative examples 1 and 2, the thickness of the layer b in the comparative example 1 is too thick, the water permeating through the cross section is much, and the peeling strength and the insulating property are certain under normal temperature and humidity conditions, but in a high-temperature and wet environment, the excessive water enters and destroys the layer b structure, the peeling strength and the insulating property are low, and the punching depth is greatly reduced; comparative example 2 has a b-layer thickness too thin, low cohesive strength, various properties are reduced, and a thickness too thin, pin holes may be generated during co-extrusion, and the depth of drawing may be greatly reduced.

Comparative example 3

The outer base material resin layer 1 is a co-extrusion structure with 3 layers of a layer/b layer/c layer, wherein the layer a is PET, the layer b is acid modified polyolefin, the thickness of the layer b is 2 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.07 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.06 kv/mum. Secondly, the peel strength of the layer a/layer c is 0.8N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.4N/15mm under the test environment of 90 +/-2% at 40 ℃. Further, it was tested to have a puncture strength of 0.35N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.02 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was allowed to stand at 23 ℃ and 50% relative humidity for 24 hours, and then tested for puncture strength of 0.10N/. mu.m. In addition, the depth of the punch was 7.5 mm.

Comparative example 4

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is sulfopolyester, the thickness of the layer b is 2 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.06 kv/mum; after being placed at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.02 kv/mum. Secondly, the peel strength of the layer a/layer c is 0.9N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.2N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.38N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.01 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was allowed to stand at 23 ℃ and 50% relative humidity for 24 hours, and then tested for puncture strength of 0.10N/. mu.m. In addition, the depth of the punch was 7.5 mm.

Comparative example 5

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c and 3 layers, wherein the layer a is PET, the layer b is modified polyester elastomer, the thickness of the layer b is 2 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.07 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.06 kv/mum. Secondly, the peel strength of the layer a/layer c is 1.0N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.4N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.38N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

Comparative example 6

The outer base material resin layer 1 is a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is a modified polyester elastomer, the thickness of the layer b is 2 mu m, the layer c is nylon 6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and relative humidity of 50% for 24 hours, the breakdown voltage of the material is tested to be 0.07 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.04 kv/mum. Secondly, the peel strength of the layer a/layer c is 1N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.4N/15mm under the test environment of 90 +/-2% at 40 ℃. Further, it was tested to have a puncture strength of 0.37N/. mu.m after being left at 23 ℃ and 50% relative humidity for 24 hours.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.02 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.12N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 3 mm.

Comparative example 3, in the traditional PET/PA coextrusion method, an acid-modified polyolefin layer is arranged in the middle, polyolefin contains polar groups after acid modification, and can react with a polyamide film, and has certain adhesion, but the adhesion to crystalline polyester is relatively weak, so that the peel strength is not high as a whole, and when the water vapor enters into the environment at high temperature and humidity, the adhesion between the acid-modified polyolefin polar groups and the film is damaged, and the peel strength is greatly reduced. Because the peel strength between PET/PA is low, the PET/PA is stretched and delaminated during drawing, the drawing depth is low, and the puncture strength is also low. Meanwhile, the acid modified polyolefin is not the same resin as the crystalline polyester and the polyamide, and the polyester and the polyamide are separated by the middle layer of the polyolefin, so that the breakdown voltage is not improved.

Comparative example 4, the middle of the PET/PA co-extrusion is a layer of sulfogroup-containing polyester, although the sulfogroup-containing polyester can be well dissolved and bonded with the crystalline polyester film because of being polyester, the sulfogroup-containing polyester has certain bonding property, theoretically, the sulfogroup is a polar group and can have certain bonding property on polyamide, but the sulfogroup is a group which is easy to absorb water and hydrolyze, and can be hydrolyzed easily in the environment to lose the bonding property, so the actual peeling strength is not high, and when the PET/PA co-extrusion is carried out in a high-temperature and wet environment, the water vapor enters the polyester layer, and the peeling strength, the insulating property and the like are greatly reduced. Because the peel strength between PET/PA is low, the PET/PA is stretched and delaminated during drawing, the drawing depth is low, and the puncture strength is also low.

In comparative examples 5 and 6, a layer of modified polyester elastomer is arranged in the middle of the PET/PA co-extrusion, the modified polyester elastomer can be well dissolved and bonded with a crystalline polyester film because the modified polyester elastomer is polyester, has certain bonding property to polyamide because of modification, but is relatively weak, so that the peeling strength is not high as a whole, and when the PET/PA co-extrusion is carried out in a high-temperature and wet environment, the bonding between the polyester elastomer and the polyamide is damaged due to the entry of water vapor, and the peeling strength is reduced. Because the peeling strength between PET/PA is low, the PET/PA is stretched and layered during punching, the punching depth is low, the puncture strength is also low, and the puncture voltage is not improved for the same reason.

Comparative example 7

The outer base material resin layer 1 is of a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is composed of a mixture of acid modified polyolefin and sulfopolyester, the mixing ratio of the acid modified polyolefin to the sulfopolyester is 1:9, the thickness of the layer b is 2 mu m, the layer c is aromatic polyamide MXD6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and relative humidity of 50% for 24 hours, the breakdown voltage of the material is tested to be 0.1 kv/mum; after being placed at 40 ℃ and relative humidity of 90% for 24h, the breakdown voltage of the material is tested to be 0.06 kv/mum. Secondly, the peel strength of the layer a/layer c is 1.2N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.5N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.45N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours.

The intermediate metal layer 3 is a 50 μm annealed nickel-plated iron foil, the surface of which is plated with a 1 μm thick nickel layer, and both surfaces of which are subjected to an anti-corrosion treatment with an anti-corrosion solution.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.04 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was allowed to stand at 23 ℃ and 50% relative humidity for 24 hours, and then tested for puncture strength of 0.13N/. mu.m. In addition, the depth of the punch was 4 mm.

Comparative example 8

The outer base material resin layer 1 is of a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is composed of a mixture of acid modified polyolefin and modified polyester elastomer, the mixing ratio of the acid modified polyolefin to the modified polyester elastomer is 1:9, the thickness of the layer b is 2 mu m, the layer c is aromatic polyamide MXD6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and relative humidity of 50% for 24 hours, the breakdown voltage of the material is tested to be 0.1 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.06 kv/mum. Secondly, the peel strength of the layer a/layer c is 1.2N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.5N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.45N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours.

The high-forming gold-plastic composite film is formed by laminating the outer base material resin layer 1, the intermediate metal layer 3 and the internal heat welding resin layer 5 by the method. The breakdown voltage of the high-molding gold-plastic composite film is tested to be 0.04 kv/mum after the high-molding gold-plastic composite film is placed for 24 hours at the temperature of 23 ℃ and the relative humidity of 50%. Next, it was tested for puncture strength of 0.13N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours. In addition, the depth of the punch was 4 mm.

Comparative example 9

The outer base material resin layer 1 is of a co-extrusion structure with a layer a/a layer b/a layer c 3, wherein the layer a is PET, the layer b is composed of a mixture of acid modified polyolefin, polyester containing sulfo groups and modified polyester elastomer, the mixing ratio of the acid modified polyolefin, the polyester containing sulfo groups and the modified polyester elastomer is 2:9:9 in sequence, the thickness of the layer b is 2 mu m, the layer c is aromatic polyamide MXD6, and the layer a, the layer b and the layer c form the outer base material resin layer 1 in a co-extrusion mode. Outer base resin layer 1 thus formed: after the material is placed at 23 ℃ and 50% of relative humidity for 24 hours, the breakdown voltage of the material is tested to be 0.1 kv/mum; after being left at 40 ℃ and 90% relative humidity for 24h, the breakdown voltage of the material is tested to be 0.06 kv/mum. Secondly, the peel strength of the layer a/layer c is 1.2N/15mm at 23 ℃ under the test environment with the relative humidity of 50 +/-5%; the relative humidity is 0.5N/15mm under the test environment of 90 +/-2% at 40 ℃. In addition, it was tested to have a puncture strength of 0.45N/. mu.m after being left at 23 ℃ at a relative humidity of 50% for 24 hours.

Compared with the prior art, the PET/PA co-extrusion is carried out by a layer of acid modified polyolefin and sulfo-containing polyester or modified polyester elastomer blend or a blend of the acid modified polyolefin and the sulfo-containing polyester or modified polyester elastomer blend in the middle of the PET/PA co-extrusion, because the polar group of the acid modified polyolefin has certain adhesiveness with the polyamide film, and the sulfo-containing polyester and modified polyester elastomer are mutually adhered with the crystalline polyester film, the adhesiveness is improved, but the acid modified polyolefin, the sulfo-containing polyester and the polyester elastomer are mutually insoluble substances and have phase separation, and in addition, the polyolefin and the polyester elastomer have low cohesive strength, so the peeling strength is improved in a limited way, and when the water vapor enters a high-temperature wet environment, the adhesion among the polar groups is damaged, and simultaneously, the water vapor enters a phase separation space, and the peeling strength is greatly reduced. The depth of penetration and puncture strength did not show the desired results because of phase separation of the b layer and low cohesive strength. Also, the breakdown voltage is only marginally increased and not increased because of the presence of phase separation.

All the a-layer thicknesses in examples 1 to 11 and comparative examples 1 to 9 were 3 μm and all the c-layer thicknesses were 20 μm.

Claims

1. A high formability gold-plastic composite film is characterized in that: comprises an outer base material resin layer, an intermediate metal layer and an internal heat welding resin layer; the outer base resin layer has at least a multi-layer co-extrusion structure of a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer), wherein,

2. The highly moldable composite gold/plastic film according to claim 1, wherein: the anti-corrosion coating also comprises a first anti-corrosion layer formed on the side, in contact with the internal heat welding resin layer, of the intermediate metal layer.

3. The high formability gold-plastic composite film according to claim 2, wherein: the first anti-corrosion layer is arranged on the inner heat welding resin layer; and a second adhesive layer is arranged between the outer substrate resin layer and the middle metal layer.

4. The highly moldable composite gold/plastic film according to claim 1 or 3, wherein: and a second anti-corrosion layer is arranged on one side of the middle metal layer, which is in contact with the second adhesive layer or the outer base material resin layer.

5. The highly moldable composite gold/plastic film according to claim 1, wherein: the total thickness of the a layer/b layer/c layer co-extrusion structure is less than 50 μm.

6. The highly moldable composite gold/plastic film according to claim 1, wherein: in the multilayer co-extrusion structure consisting of the a layer/b layer/c layer, the b layer is formed by a single layer or multiple layers.

7. The high formability gold-plastic composite film according to claim 6, wherein: when the layer b contains an acid-modified polyolefin and at least one of a modified polyester elastomer and a sulfo-containing polyester, the layer b is composed of a plurality of layers, and the acid-modified polyolefin is in contact with the layer c.

8. The highly moldable composite gold/plastic film according to claim 7, wherein: when the layer b contains acid modified polyolefin, modified polyester elastomer and sulfopolyester, the layer b is of a multilayer structure of acid modified polyolefin/modified polyester elastomer/sulfopolyester or a multilayer structure of acid modified polyolefin/(a blending layer of modified polyester elastomer and sulfopolyester), and the acid modified polyolefin is at the side contacting with the layer c.

9. The highly moldable composite gold/plastic film according to claim 8, wherein: the layer b contains acid modified polyolefin, modified polyester elastomer and sulfopolyester, the layer b is a multilayer structure of acid modified polyolefin/(modified polyester elastomer and sulfopolyester blended layer), and the thickness of the layer b is 1-3 μm when the acid modified polyolefin is in contact with the layer c.

10. The highly moldable composite gold/plastic film according to claim 6, wherein: when the layer b contains the modified polyester elastomer and the sulfo-containing polyester and does not contain the acid-modified polyolefin, the layer b is composed of a single layer or a plurality of layers.

11. The highly moldable composite gold/plastic film according to claim 10, wherein: when the layer b is composed of a single layer, the single layer is a blended layer of the modified polyester elastomer and the sulfogroup-containing polyester.

12. The highly moldable composite gold/plastic film according to claim 10, wherein: when the layer b is composed of a plurality of layers, each layer of the plurality of layers is a blend layer of the modified polyester elastomer and the sulfopolyester.

13. The highly moldable composite gold-plastic film according to any one of claims 1 to 12, wherein: the peeling strength between the layer a and the layer c is more than 2.6N/15mm in terms of peeling speed of 50mm/min under the environment that the temperature is 23 ℃ and the relative humidity is 50% +/-5%.

14. The highly moldable composite gold-plastic film according to any one of claims 1 to 12, wherein: the peeling strength between the layer a and the layer c is more than 1.0N/15mm in terms of peeling speed of 50mm/min under the environment that the temperature is 40 ℃ and the relative humidity is 90% +/-2%.

15. The highly moldable composite gold-plastic film according to any one of claims 1 to 12, wherein: the high-formability gold-plastic composite film is placed for 24 hours in an environment with the temperature of 23 ℃ and the relative humidity of 50 +/-5 percent, so as to

Electrode cylinder and

the dielectric breakdown voltage of the highly moldable composite gold-plastic film is 0.1kV/μm or more in the total thickness thereof by applying breakdown at a voltage rising rate of 0.3 kV/sec.

16. The highly moldable composite gold-plastic film according to any one of claims 1 to 12, wherein: the high-formability gold-plastic composite membrane is placed for 24 hours under the environment that the temperature is 23 ℃ and the relative humidity is 50 +/-5%, a puncture strength test is carried out by using a test needle with the front end R0.5mm at a test speed of 50mm/min, and the puncture strength relative to the total thickness of the high-formability gold-plastic composite membrane is more than 0.15N/mum.

17. The high formability gold-plastic composite film according to any one of claims 1 to 12, wherein: the punching depth of the high-formability gold-plastic composite film is 4.5-10.0 mm.

18. The highly moldable composite gold/plastic film of claim 13, wherein: the peeling strength between the layer a and the layer c is more than 3.2N/15mm in terms of peeling speed of 50mm/min under the environment that the temperature is 23 ℃ and the relative humidity is 50% +/-5%.

19. The highly moldable composite gold/plastic film according to claim 14, wherein: the peeling strength between the layer a and the layer c is more than 1.9N/15mm in terms of peeling speed of 50mm/min under the environment that the temperature is 40 ℃ and the relative humidity is 90% +/-2%.

20. A laminate, characterized in that: the laminated body is used as an outer base material resin layer and applied to the gold-plastic composite film; the laminate has a multilayer co-extrusion structure of at least a polyester layer (a layer)/an adhesive layer (b layer)/a polyamide layer (c layer), wherein,

21. The laminate according to claim 20, wherein:the laminated body is placed for 24 hours in an environment with the temperature of 23 ℃ and the relative humidity of 50% +/-5% so as to

Electrode cylinder and

the electrode cylinder of (1) is pinched, and breakdown is performed at a voltage increase rate of 0.3kV/sec, and the dielectric breakdown voltage with respect to the thickness of the laminate is 0.23kV/μm or more.

22. The laminate according to claim 20, wherein: the laminated body is placed for 24 hours in an environment with the temperature of 40 ℃ and the relative humidity of 90% +/-2% so as to

Electrode cylinder and

the breakdown is performed at a voltage increase rate of 0.3kV/sec, and the dielectric breakdown voltage with respect to the thickness is 0.15kV/μm or more.

23. The laminate according to claim 20, wherein: the laminate was left to stand at a temperature of 23 ℃ and a relative humidity of 50% +/-5 for 24 hours, and then a puncture strength test was carried out at a test speed of 50mm/min using a test needle having a tip R0.5mm, and the puncture strength with respect to the thickness was 0.65N/. mu.m or more.

24. A battery, characterized by: a battery pack comprising the highly moldable composite gold-plastic film according to any one of claims 1 to 19.